Addition polymers with polyethylenimine terminal groups

ABSTRACT

Polymers represented by the general structure   WHERE R1 R2 and R4 can be hydrogen, alkyl radicals of one through four carbon atoms, -CH2CH2NH2 radicals, or -CH2CH2OH radicals; R3 and X can be hydrogen or alkyl radicals of one through four carbon atoms; Zb can be an organic linking radical; Y can be hydrogen, an alkyl radical of one through four carbon atoms, an alkenyl radical of two through six carbon atoms, -CN, halogen, phenyl, -OR,   where R is an alkyl radical of one through 18 carbon atoms; D is an end group such as hydrogen, alkyl or alkenyl; A IS A NUMBER 1 THROUGH 2000; B IS 0 OR 1; AND C IS A NUMBER 5 THROUGH 5000; THE C/A QUOTIENT BEING GREATER THAN 1.

United States Patent [191 [111 3,864,379

Thompson Feb. 4, 1975 ADDITION POLYMERS WITH [57] ABSTRACT POL ET TERMINAL GROUPS Polymers represented by the general structure R ERS R x I i I I I 2 t I R I-I-CH-CH2N%-Z 'CH2-C|--D ---a hi I c Y [75] Inventor: Darrell R. Thompson, Somerville, where N]. R R and R can be hydrogen, alkyl radicals of one through four carbon atoms, -CH CH NH [73] Assrgnee. E. I. du Pont de Nemours and radicals or 2 2 radicals;

Company Wilmington R and X can be hydrogen or alkyl radicals of one [22] Filed: Apr. 5, 1972 through four carbon atoms;

Z, can be an organic linking radical; [211 App! 24l400 Y can be hydrogen, an alkyl radical of one through Related U.S. Application Data four carbon atoms, an alkenyl radical of two [63] Continuation-in-part of Ser. No. 776,751, Nov. 18, h gh six carbon m CN h log n, phenyl,

1968, abandoned. OR,

[52] U.S. Cl. 260/465.4, 260/47 R, 260/67.6 R, i? or 9 260/70 R, 260/70 M, 260/465 D, 260/471 C,

260/482 R, 260/553 R, 260/570.5 P, 260/570.8 R, 260/583 R, 260/583 G, where 260/583 H, 260/583 P, 260/584 R, 260/584 A R is an alkyl radical of one through 18 carbon [51] Int. Cl. C07c 121/34, C07c 121/42 atoms; [58] Field of Search 260/465.4, 465.5, 465 D, D is an end group such as hydrogen, alkyl or 260/465 E alkenyl;

a is a number 1 through 2000; [56] References Cited b is 0 or 1;

UNITED STATES PATENTS and 3,465,036 9/1969 Dundon et al. 260/465.4 x C 1S a number 5 through 5000;

the c/a quotient being greater than 1. Primary Examiner-loseph P. Brust 9 Claims, N0 Drawings ADDITION POLYMERS WITH POLYETHYLENIMINE TERMINAL GROUPS CROSS-REFERENCE TO RELATED s APPLICATIONS This application is a continuation-in-part of Ser. No. 776,75l, filed Nov. 18, 1968 and now abandoned.

STATEMENT OF THE INVENTION This invention relates to addition polymers. It is more particularly directed to addition polymers represented by the structure I R 13?" R2 N CH one N :l;

where R R and R can be hydrogen, alkyl radicals of 1 through 4 carbon atoms, -CH CH NH radicals or -CH CH OH radicals;

R and X can be hydrogen or alkyl radicals of I through 4 carbon atoms;

2,, can be organic linking radical;

Y can be hydrogen, an alkyl radical of 1 through 4 carbon atoms, an alkenyl radical of 2 through 6 carbon atoms, CN. halogen, phenyl, -OR,

the /41 quotient being greater than I.

UTlLlTY The polymers of the invention are useful as filmformers in coating compositions, particularly when combined with a second polymer having complementary reactive groups. Illustrative of such second polymers are heat-reactive phenolics, polyglycidy] ethers and esters, polyisocyanate resins, butylated urea/formaldehyde resins and melamine formaldehyde/alkanol resins.

The polymers of the invention can be used as filmformers by mixing from about 55 to about 95 parts of the polymer with from about to 45 parts ofthe second complementary polymer, in a suitable solvent. This solution can then be used directly to give clear coatings, or it may be pigmented as desired.

The coating composition can be applied conventionally and preferably is then baked for from about to minutes at 80200 C.

The polymers of the invention are also useful as aids for dispersing solid particles in organic liquids. They are especially useful as aids for dispersing pigments in organic liquids. Illustrative of the pigments which can be dispersed are titanium dioxide. carbon black, zinc oxide, lead titanate, potassium titanate, antimony oxide, lithopone, phthalocyanine blue. toluidine red, quiinacridone and the like.

Pigment dispersions made with polymers of the invention are remarkably resistant to flocculation, which gives the paints into which the dispersions are incorporated higher initial gloss, better hiding and tinting strength. and makes them resistant to color drift and gloss loss. These pigment dispersions can also be used satisfactorily with many more diverse types of paints than conventional pigment dispersions. Moreover, a dispersion made with a polymer of the invention can have a significantly higher pigment content. while retaining the same degree of fluidity. than when conventional aids are used.

The polymers of the invention can be used as pigment dispersing aids by dissolving from 0.00] to about 2.00 grams of polymer per square meter (Measured by the Brunauer, Emmett and Teller nitrogen adsorption method described on page 30 of Colloidal Dispersions" by Earl K. Fischer, published by John Wiley and Sons in I950.) of surface area of the pigment to be used. preferably 0.004 to about 0.100 gram per square meter, in an organic liquid compatible with the paint into which the pigment dispersion is to be incorporated. lllustrative of organic liquids which can be used are aliphatic and aromatic hydrocarbons, ethers, esters, ketones, alcohols, and mixtures of these.

An appropriate amount of pigment is then added to this solution, which is then subjected to shear, as by sand-grinding or ball-milling, to deagglomerate and disperse the pigment. This pigment dispersion or mill-base can be then added directly to a paint.

Polymers of the invention preferred for use as pigment dispersing aids are those of formula (1 where a is 3 through and c is 20 through 500. Especially preferred are those whose preparation is shown in the Examples.

PREPARATION OF THE POLYMERS Preparation of the polymers of the invention can be more easily described if it is first explained that structurally the polymer molecule divides itself naturally into two or three segments.

The first of these, the

CHg-C CH-CHg-N Ra-N segment, is derived from a polyethylenimine.

The precursors to these segments are separately prev pared and then linked together by reacting them under H2 N z apropriate conditions to form the polymers of the invention. A. Preparation of the Addition Polymer 5 This precursor can be prepared by polymerizing one 2 2 or more of such monoethylenically unsaturated mono- HS CH2COOH mers as esters of acrylicor methacrylic acids with alkanols of one through 18 carbon atoms. acrylonitrile. methacrylonitrile, vinyl esters such as vinyl acetate, HS CHZCH2COOH vinyl chloride, vinyl fluoride, vinyl ethers, ethylene. propylene, isobutylene, styrene and methyl vinyl ketone. Diene monomers such as butadienes, chloroprene and isoprene can also be used.

Because the precursor segments are separately pre- 5 pared and then chemically linked together, the addition polymer must bear a functional group which can react and Polymerization can be carried out using conventional solution, emulsion. bead or bulk polymerization methods. Solution polymerization is preferred.

In the preferred method. polymerization is con' ducted in a solvent such as toluene, benzene. acetone.

with either the linking radical or di tl with ethyl acetate. tetrahydrofuran, or mixtures of these. the The monomer concentration in the solvent can range 20 from 5% by weight to about 100%. preferably 20-3071. The polymerization temperature can range from about R R3 R C. to about l50 C. Polymerization is preferably carried out in an oxygen-free atmosphere and is com- R2 N CH CH2 N segmentplete in from I 100 hours, usually 3 to 18 hours.

a 25 The resulting addition polymer can be reacted directly with the other components of the polymer mole- Because of this, polymerization is conducted in the Cule. presence of from .0l% to about 10% (by weight) of a B preparation f the polyethylenimine free radical initiator not only induces polymersome of the polyethylenimines are available comiZflIlOfl but also introduces a terminal functional group mercially (Diethylene triamine, triethylene tetramine into the resulting P y moleculeand tetraethylene pentamine are sold by the Commerlllustrative of such free radical polymerization initiai S l Corporation P l h l i i h vi tors re average molecular weights of 600-l ,200 and 1,800 are 4,4-azobis-4-cyan0pentan0ic a sold by the Dow Chemical Company as Montrek" res- 4. '11Z0his-4-cyanopentanoyl chloride ins.) and can he used directly. without processing. 4,4'-azohis-4-cyanopentanol Those polyethylenimines which cannot be obtained and commercially can he prepared according to the general bis( l-hydroxycyclohexyl) peroxide. equation R R Heat $1 3 3 2 NH aH /CHZ Pressure R2 -N CH-CH -N a The addition polymer bearing the functional group where R R R R and a are as in formula (1). can also be prepared by conducting the polymerization C. Linking the Addition Polymer to the Polyethylen' in the presence of 0.l 10%, preferably 0.5%, ofa suitimine ably substituted chain transfer agent and the usual The polymers of the invention are made by coupling amount of a conventional free radical initiator such as together the previously prepared addition polymer and benzoyl peroxide or azobisisobutyronitrile. polyethylenimine. if the functional group on the addilllustrative of the chain transfer agents which can be tion polymer can react directly with the polyethylenused are imine, they can be coupled together by simply mixing stoichiometric amounts of each in a vessel and then .'"1 a holdin them at a tem erature of 0 to C. for from HOCHZ/LT f 0 u CHZOH H2 hours P If a functional group on the addition polymer cannot r react directly with the polyethylenimine, either may be Hoot: .t COOH modified by reacting it with an appropriate linking 05 compound so that it will react. Preferably the addition polymer is so modified.

Illustrative of such a reaction (which will introduce r 3H ocN CH NCO 9 r 0 0 an cs HzN-A B-OC-NH s woo I F 0 o NaOH (2 B OH Cl-CHz-CH CH2 B-O-CH2-CH OH; HCl

Q 1-: O cH -CH CH2 HEN A B-O-CH2-CHCH2-NH-A ll ll e-o-c- H N-A ----9 8-0-6 Q SO -NH-A HC].

0 0 O O Na CO B-C ClCH2CH-CH2 B-C-O-CHgCH-CH HCl O O O n n In these equations, B signifies the addition polymer segment and A signifies the polyethylenimine segment. After one of the precursors has been reacted with the linking compound, the product and the other precursor are dissolved in a mutual solvent such as toluene andsolid. The polymers are soluble in common organic liquids such as toluene, ethyl acetate, tetrahydrofuran, acetone, hexane, cyclohexane and dimethylformamide.

PREFERRED EMBODIMENTS OF THE INVENTION The following examples are submitted so that the invention may be more readily understood and practiced.

Those skilled in the art will no doubt be able to compose numerous variations on their central theme, such as the attachment of innocuous substituents. It is naturally considered that these variations are a part of the invention.

In the examples all parts are by weight unless otherwise indicated.

EXAMPLE 1 The solution was stirred under a nitrogen blanket and refluxed for 2 hours. It was then cooled and added dropwise to a rapidly stirred solution of 15 parts of Montrek 6 (Montrek 6 is polyethylenimine with a To a dry bottle which had been flushed with nitrogen molecular weight of about 600, sold by Dow Chemical were added 75 parts of methyl methacrylate (filtered C0mpany-) (polyethylenimine) and 100 parts of anhythrough alumina), 150 parts of toluene, 0.75 part of drous dimethylformamide. The resulting solution was 'azodiisobutyronitrile, and 0.75 part of 2-mercapt0estirred for an additional 30 minutes and allowed to thanol. m stand overnight.

The bottle was capped and placed in a constant tem- The solution was then reduced to one-half its original perature bath, where it was held for 18 hours at 70 C. volume by heating under vacuum. The polymer was The resulting polymer was precipitated in methanol, precipitated by pouring it into 2,500 parts of methanol. collected by filtration and dried at 60 C. under vac- The precipitated polymer was collected on a filter, disuum. solved in 100 parts of dimethylformamide and again Ten grams of this polymer in 50 parts of benzene precipitated by pouring it into 2,500 parts of methanol. were added, under anhydrous conditions over a 1 hour The product was isolated by filtering it off and then period, to a rapidly stirred refluxing solution of 0.326 drying it under vacuum at 60 C. This gave 45.] parts part of toluene diisocyanate, 2 drops of dibutyl tin diof polymer having the structure 0 CN ca, 1 H H I I I HN CHzCHzN C CHzCHz 3 CH2 3 H CH o i l 0011;, u l,

laurate and 20 parts of benzene. The resulting solution where c' is about 500. was then refluxed for l hour and cooled.

Eighteen hundredths part of N(2-ammoethyl) azm EXAMPLE 3 dine was added to the solution, which was then allowed to stand overnight. Two-tenths part of N.N-dimethyl To a dry bottle which had been flushed with nitrogen ethylene diamine was added, the solution refluxed for were added 41 parts of methyl methacrylate, 9 parts of 2 hours and then cooled.

The resulting solution of polymer having the structure CH3 o o I H II ll H3O N cagcnzn c N N-C-OCHzCHgS where c is about 50,

can be used directly in the preparation of pigment disand nitrogen inlet were charged 200 parts of dry benzene, parts of methyl methacrylate (filtered through alumina) and 2 parts of 4,4-azobis-4-cyanopentanoyl chloride.

butyl acrylate, 1.5 parts of 4,4-azobis-4- cyanopentanoyl chloride and parts of toluene.

The bottle was capped and placed in a constant temcu l CH2 c oca ' polymer having the structure CH 0 CN H CH I H I I I H C-N CH CHEN C-CH2CH2C CHz-C CH -C w H I I I 3 CH C 0 C 0 I I O- (CH2 )3CH3 OCHS where C D is about 500 and the addition polymer The resulting polymeric acid chloride was then dissegment is a random copolymer. solved in 60 parts of dry benzene and divided into two equal portions. One portion (A) was added dropwise to EXAMPLE 4 a solution of 5 parts of triethylenetetramine in 50 parts A solution of 2.5 parts of 4,4'-azobis-4- ot'benzene; the other portion (B) was added to parts cyanopentanoyl chloride, parts of anhydrous benof Montrek 6. zene and 90 parts of butyl acrylate was added over 11 l The resulting polymers were isolated from solution hour period to 208 parts f refluxing anhy r nby precipitating them from methanol and then drying zc H) them at 60 C. under vacuum.

This solution was then refluxed in a nitrogen atmo The polymers had the structure 0 CN H u I i H H H an CHzCHz 043126524 CH2 a CH O O l CH2- H CH2 )3-CH CH CH sphere, with stirring, for 3 hours. The solution was 25 where a is 3 for (A) and 14 for (B). cooled and added to 10 parts oftriethylenetetramine in 100 parts of dry benzene, with vigorous stirring, at EXAMPLE 6 room temperature, The resulting polymer was precipi- A solution of 1.5 parts of 4,4-azobis-4- tated in methanol and dried in a vacuum oven. lt had cyanopentanoyl chloride in 90 parts of vinyl acetate the structure was added, dropwise over a 30-minute period and 0 CN H H H l I I HN CHzCHzNj- C CH2CH2-C CH2 C H l l 3 CH 0 o I 0(CH CH where c is about 500. under a nitrogen blanket, to 200 parts of stirred refluxing benzene. After addition, the solution was refluxed EXAMPLE 5 for an additional 2 hours and then cooled to room tem- A flask fitted with a stirrer. nitrogen inlet and conpemwm denser drying tube was Charge with 90 Parts Of The resulting polymer solution was then added over ethylhexyl acrylate (filtered thmugh fllumlna), a 30-minute period to 15 parts of triethylenetetramine Part5 of4t4"alobis'4'cyanopentan0i: field, Parts of in parts of benzene, at room temperature. This reac- Z-mercaptoacetic acid and 207 parts of benzene. The on mixture was Stirred for 30 minutes. solution was stirred and refluxed under nitrogen for 4 50 The resumng polymer was purified by precipitation hoursfrom anhydrous ether and then dried at C. under The resulting solution was poured into 3,000 parts of vacuum in a nitrogen atmosphere methanol to pricipitate the polymer, which was isolated The pow",er had the Structure 0 CN H H H II I I HN Cl l Cl'lzl fl- C CH2CH2-C CH2 C H l I i 3 CH3 o-g-ca by filtering it and then drying it in vacuum desiccator where c is about 500. over concentrated sulfuric acid.

A mixture of 10 parts of this polymer and a 10 mol EXAMPLE 7 I excess of thionyl chloride were refluxed for 24 hours. To a dry bottle which had been flushed with nitrogen The excess thionyl chloride was then removed by distilwere added 45 parts of styrene (distilled), 0.23 part of lation under reduced pressure. 4,4-azobis-4-cyanopentanoyl chloride and 104.8 parts of toluene. The bottle was capped and placed in a con- The tube was opened and unpolymerized vinyl chlostant temperature bath. where it was held for 15 hours ride removed by distillation. at 70 C. B. A flask was charged with 8.6 parts of N-(2-amino- The resulting polymer solution was added over a 30- ethyl)aziridine. l7.2 parts of N.N- minute solution of3 parts oftriethylene tetramine in 30 5 dibutylethylenediamine and 100 parts of anhydrous diparts of toluene, at room temperature. methylformamide. The solution was refluxed under an The resulting polymer was isolated by precipitating it anhydrous nitrogen'atmosphere for 4 hours. i metha ol a d th n dryi i t 60 C, under vacuum This solution was then distilled under reduced pres- Th p|ymer h d h Structure sure to remove solvent and unreacted starting material.

(P CN H H H HN CHQCHZN C-CHgCHg-C CH -C H I 5 CH3 I where c is about 200. leaving the product, N.N-dibutyltriethylenetetramine,

EXAMPLE 8 as a slightly yellow liquid.

C. To 2.44 parts of the N,N-dibutyl triethylenetetramine in 30 parts of dimethylformamide was added solution (A), over a period of 30 minutes, at room temperature. The solution was stirred for an additional 1 hour and the resulting polymer then isolated by precipitation in methanol.

To a flask were added 300 parts of anhydrous diethyl ether, 67.6 parts of polyisobutylene (molecular weight about 2.700) and 4.5 parts ofsilver cyanate. These materials were stirred into a slurry which was then cooled in an ice bath.

Seven and six-tenths parts of iodine were added.

whereupon the solution turned dark brown and a yel- The polymer thus isolated was then dried in a vaclow precipitate formed. The mixture was stirred and reuum oven at 60 C. lt had the structure CH (CH2 0 CN N {lCH CHzN C CH CH C CH C H I I CH (CH2 )3 6 CH3 (:1

fluxed for 2 hours. cooled and then filtered. where 0 is 50 500.

The solution was then added over a -minute period to a refluxing solution of 100 parts of anhydrous diethyl 4O EXAMPLE 10 ether and parts of triethylenetetramine. Refluxing was continued for 3 hours and the solution was then cooled. To a polymer tube were added 25 parts of cyclohex- The resulting polymer was isolated by precipitating it ane, 0.30 part of 4,4'-azobis-4-cyanopentanoyl chlotwice from methanol and then drying it under vacuum ride and 5 parts of vinyl acetate. The solution was deat 60 C. for 24 hours. gassed to remove oxygen and then cooled to about The polymer had the structure 40 C. with a dry ice-acetone mixture. Ten parts of 0 CH H CH H H H I I I HN [:CH2CH N C NC C C-Cll H I I I CH 1 CH where c is about 50. vinyl chloride were then condensed in the tube, which was then sealed. EXAMPLE 9 The polymerization was run in a constant tempera- A. To a polymer tube were added 25 parts of cycloture bath at 55 C. for 36 hours. The tube was then hexane and 0.30 part of 4.4'-azobis-4-cyanopentanoyl opened and the solution inside was slowly added to 5 chloride. The solution was degassed to remove oxygen parts of poly(N-methyl propylenimine) (molecular and cooled to about -40 C. with dry ice-acetone mixweight 710) in parts of anhydrous dimethylformture. amide, over a 30-minute period, at room temperature.

Fifteen grams of vinyl chloride were condensed in the The reaction mixture was stirred for an additional hour tube, care being taken to avoid contamination with ox- ,5 at room temperature. The resulting polymer was isoygen and water. The tube was sealed and allowed to lated by precipitating it in methanol and was then dried warm to room temperature, then placed in a constant in a vacuum at 60 C.

temperature bath at C. and held there for 36 hours. The polymer had the structure CH3 CH3 en H I H HN- CHCH2 N C-CHzCHg-C c112- C D is about 50 and the addition polymer segment is a random copolymer.

EXAMPLE ll To 208 parts of refluxing benzene were added, over a one-hour period and under a nitrogen atmosphere, )0 parts of VV ll) (VV l0 vinyl monomer is the vinyl ester of a saturated tertiary 10 carbon atom carboxylic acid sold by the Shell Chemical Company.) vinyl monomer containing l.5 parts of 4,4'-azobis-4-cyanopentanoyl chloride. The solution was then refluxed for another 5 hours and cooled.

One portion was added to a solution of parts oftriethylenetetramine in 40 parts of anhydrous benzene.

The solution was then poured into methanol to precipitate the resulting polymer, which was filtered off and dried in a vacuum oven at 60 C. i

I claim:

1. A polymeric material of the formula R ,3 5 Rz'N H-CH2-N ag g D where R,, R and R are hydrogen or alkyl radicals of I through 4 carbon atoms.

R and X are hydrogen or alkyl radicals of I through 4 carbon atoms;

Z]; is 21 0 CN 11 I -C-CH2CH2C- radical;

radical;

Y is an alkyl radical of I through 4 carbon atoms. halogen.

CH3 M O I II H H l C CH C l. H l 2 I t 0 01 l I r c o l l CH C D o H OCl l5 -C-OR where 5 R is an alkyl radical ofone through 18 carbon atoms;

D is hydrogen; a is a number I through 2000', h is 0 or 1; and 3t) 0 is a number 5 through 5000;

the c/u quotient being greater than I.

2. The polymeric material of claim 1 wherein a is a number 3 through 100, and

c is a number 20 through 500.

3. The polymeric material of claim 2 having the formula l0 ca caz H I II rm TCHZCHQN where c is about 500.

4. The polymeric material of claim 2 having the formula CN H l CH3 i v 1 l caacayc CHg-C CH2 C 3+ I I I g CH3 II c o C I l l O CH2 )sCHg OCH 7 .l

1 l N C mo 2 H C 2 H C On C 9 7 4 6 3 n C -itwlr m LL 11 a l .HgCHzN j" 3 where C D is about 500 and the addition polymer where l is about 500. segment is a random copolymer.

8. The polymeric material of claim 2 having the formula 5. The polymeric material of claim 2 having the for mula a w H HN CHzCHzN JP, CH3

C CHaCHa C H CH CH N CH3 (CH2 )3 where c is -500.

where c is about 500.

6. The polymeric material of claim 2 having the for- Y 9. The polymeric material of claim 2 having the formula H IIN CH2 -CH(CH )QCHS CH2 CH3 ll UN 7. The polymeric material of claim 2 having the formula 

1. A POLYMERIC MATERIAL OF THE FORMULA
 2. The polymeric material of claim 1 wherein a is a number 3 through 100, and c is a number 20 through
 500. 3. The polymeric material of claim 2 having the formula
 4. The polymeric material of claim 2 having the formula
 5. The polymeric material of claim 2 having the formula
 6. The polymeric material of claim 2 having the formula
 7. The polymeric material of claim 2 having the formula
 8. The polymeric material of claim 2 having the formula
 9. The polymeric material of claim 2 having the formula 